Chemistry in an inorganic -organic hybrid aerogel: Chitosan-silica aerogel

2005 2005

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Abstract (summary)

In this thesis, chemistry in a nanoporous inorganic-organic hybrid aerogel (X-silica aerogel) has been explored. The aerogel typically consisted of 10%w/w bioderived polymer (chitosan), and 90%w/w inorganic silica, which interact at the molecule level. The aerogel has a low density in the range of 0.2–0.3 g/cm3, high surface area in the range of 500–950m 2/g, and large pore volume about 90%. The pores are about 3–5 nm in diameter and the size of the primary particles comprising the aerogel network is about 1.5nm.

Chemical studies of X-silica aerogels were carried out in the first instance with organic molecules, including dansyl chloride (DC), succinic anhydride (SA), bis(4-isocynatocyclohexyl) methane (HMDI), and isocyanatoethyl methacrylate (IEMA). These reactions lead to modified X-silica aerogel products imparted with valuable functionalities, including fluorescence, carboxylic acid groups, and pendant isocyanate and methacrylate groups. The functionalized aerogels then were utilized to form novel composites. The isocyanate functionalized aerogels were combined with amine-containing silicone polymers to produce aerogel-silicone polymer composites, and methacrylate functionalized aerogels were reacted with hydroxyethylmethacrylate (HEMA) monomer to produce aerogel-polyHEMA composites.

The chemical studies were extended to gold-ion Au(III)-X-silica aerogels. Photoreduction of the Au(IIl)-X-silica aerogels by UV irradiation at 254nm reduced the Au(III) ions into Au(0) nanoparticles (AuNPs) while oxidizing the chitosan. Various sizes of AuNPs, with mean diameters from 8–87nm were obtained by varying the Au(III) ions concentration in aerogels from Au(III)/-NH 2 (-NH2 amine groups on chitosan) ratio 1:120 to 1:5. The intensity and time of exposure to the UV light were varied to explore their effect. Two dimensional patterns of Au(0)-X-silica aerogels were achieved by UV irradiation through a mask. Photo-reduction of Au(III)-X-silica aerogels in the presence of various thiols and disulfides leads to functionalized Au nanoparticles by the strong chemisorption of sulfurs and Au nanoparticles. Moreover, when these are present during the photolysis they control the growth of the gold nanoparticles.

Indexing (details)

Materials science
0488: Chemistry
0794: Materials science
Identifier / keyword
Applied sciences; Pure sciences; Aerogel; Chitosan-silica; Inorganic-organic hybrid; Silica
Chemistry in an inorganic -organic hybrid aerogel: Chitosan-silica aerogel
Liu, Xipeng
Number of pages
Publication year
Degree date
School code
DAI-B 66/05, Dissertation Abstracts International
Place of publication
Ann Arbor
Country of publication
United States
9780542128004, 0542128004
Risen, William M.
Brown University
University location
United States -- Rhode Island
Source type
Dissertations & Theses
Document type
Dissertation/thesis number
ProQuest document ID
Database copyright ProQuest LLC; ProQuest does not claim copyright in the individual underlying works.
Document URL
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